Regulated synthesis of Zr-metal–organic frameworks with variable hole size and its influence on the performance of novel MOF-based heterogeneous amino acid–thiourea catalysts

We present an efficient and easy synthesis method for incorporating organocatalytic moieties into Zr-metal organic frameworks (Zr-MOFs). The catalytic activity and selectivity of the new chiral catalysts were improved by adjusting the aperture of the MOF cavities. The hole size of the Zr-MOF was modulated by adding acid and replacing bridge ligands during synthesis. The difunctional chiral units of amino acid–thiourea are anchored onto the Zr-MOF by a mild synthesis method from an isothiocyanate intermediate which could effectively avoid the racemization of chiral moieties in the synthesis process. By means of specific surface area measurement (BET), scanning electron microscopy (SEM) and powder X-ray Diffraction (PXRD), it was confirmed that Zr-MOFs with different pore sizes were synthesized without breaking the basic octahedral structure of the MOF. Finally, good yields (up to 83%) and ee values (up to 73%) were achieved with the new heterogeneous catalysts in 48 hours for the aldol reaction of 4-nitrobenzaldehyde with acetone. By contrast, using the catalyst support without modulating the synthesis, the yield (30%) and the ee-value (26%) were both low. Experiments have confirmed the important influence on the reaction selectivity of providing a suitable reaction environment by controlling the aperture of MOF cavities.

[1]  G. Zeng,et al.  Materials Institute Lavoisier (MIL) based materials for photocatalytic applications , 2021, Coordination Chemistry Reviews.

[2]  A. Morsali,et al.  Construction of an Asymmetric Porphyrinic Zirconium Metal-Organic Framework through Ionic Postchiral Modification. , 2020, Inorganic chemistry.

[3]  M. Ghasemzadeh,et al.  Environmentally Benign One‐pot Synthesis of Benzo‐Fused Seven‐Membered Heterocyclic Compounds Using UiO‐66 Metal‐Organic Framework as Efficient and Reusable Catalyst , 2020 .

[4]  Jun Guo,et al.  Advanced photocatalysts based on metal nanoparticle/metal-organic framework composites , 2020, Nano Research.

[5]  Di Wu,et al.  L-proline functionalized pillar-layered MOF as a heterogeneous catalyst for aldol addition reaction , 2020 .

[6]  Rui Liu,et al.  Controllable synthesis of Co-MOF-74 catalysts and their application in catalytic oxidation of toluene , 2020 .

[7]  Xingpeng Guo,et al.  Metal-organic framework membranes: From synthesis to electrocatalytic applications , 2020, Chinese Chemical Letters.

[8]  D. Dubbeldam,et al.  Synthesis of Chiral MOF‐74 Frameworks by Post‐Synthetic Modification by Using an Amino Acid , 2020, Chemistry.

[9]  C. Cativiela,et al.  Stereoselective synthesis of acyclic α,α-disubstituted α-amino acids derivatives from amino acids templates , 2020 .

[10]  Dingxin Liu,et al.  Synthesis and Applications of Isoreticular Metal–Organic Frameworks IRMOFs-n (n = 1, 3, 6, 8) , 2019, Crystal Growth & Design.

[11]  Liang Shen,et al.  l-Proline functionalized metal-organic framework PCN-261 as catalyst for aldol reaction , 2019, Inorganic Chemistry Communications.

[12]  Haijun Wang,et al.  Porous Zr–Thiophenedicarboxylate Hybrid for Catalytic Transfer Hydrogenation of Bio-Based Furfural to Furfuryl Alcohol , 2019, Catalysis Letters.

[13]  Abdullah M. Asiri,et al.  Engineering UiO‐66 Metal Organic Framework for Heterogeneous Catalysis , 2019, ChemCatChem.

[14]  A. Arrieta,et al.  Organocatalysts Derived from Unnatural α-Amino Acids: Scope and Applications. , 2018, Chemistry, an Asian journal.

[15]  I. Pápai,et al.  Mechanistic Insight into Asymmetric Hetero-Michael Addition of α,β-Unsaturated Carboxylic Acids Catalyzed by Multifunctional Thioureas. , 2018, Journal of the American Chemical Society.

[16]  Shin‐ichi Hirashima,et al.  Stereoselective conjugate addition of ketones to alkylidene malonates using thiourea-sulfonamide organocatalyst. , 2018, Chirality.

[17]  Lujie Cao,et al.  Post-Synthesized Method on Amine-Functionalized MOF Membrane for CO2 /CH4 Separation , 2018, ChemistrySelect.

[18]  C. Easton,et al.  Post-Synthetic Annealing: Linker Self-Exchange in UiO-66 and Its Effect on Polymer–Metal Organic Framework Interaction , 2017 .

[19]  Linbing Sun,et al.  Metal-Organic Frameworks for Heterogeneous Basic Catalysis. , 2017, Chemical reviews.

[20]  D. Farrusseng,et al.  Enantiopure Peptide-Functionalized Metal-Organic Frameworks. , 2015, Journal of the American Chemical Society.

[21]  K. Lillerud,et al.  Synthesis and characterization of amine-functionalized mixed-ligand metal-organic frameworks of UiO-66 topology. , 2014, Inorganic chemistry.

[22]  Kimoon Kim,et al.  Homochiral metal-organic frameworks for asymmetric heterogeneous catalysis. , 2012, Chemical reviews.

[23]  Geoffrey I N Waterhouse,et al.  A general thermolabile protecting group strategy for organocatalytic metal-organic frameworks. , 2011, Journal of the American Chemical Society.

[24]  Bartolomeo Civalleri,et al.  Disclosing the Complex Structure of UiO-66 Metal Organic Framework: A Synergic Combination of Experiment and Theory , 2011 .

[25]  Seth M Cohen,et al.  Isoreticular synthesis and modification of frameworks with the UiO-66 topology. , 2010, Chemical communications.

[26]  Yan Liu,et al.  Engineering Homochiral Metal‐Organic Frameworks for Heterogeneous Asymmetric Catalysis and Enantioselective Separation , 2010, Advanced materials.

[27]  Abigail G Doyle,et al.  Small-molecule H-bond donors in asymmetric catalysis. , 2007, Chemical reviews.

[28]  Richard A. Lerner,et al.  Proline-Catalyzed Direct Asymmetric Aldol Reactions , 2000 .